CN101400640B - Method for producing 1,2-phenylethane compound using atom transfer radical coupling reaction - Google Patents
Method for producing 1,2-phenylethane compound using atom transfer radical coupling reaction Download PDFInfo
- Publication number
- CN101400640B CN101400640B CN2007800087713A CN200780008771A CN101400640B CN 101400640 B CN101400640 B CN 101400640B CN 2007800087713 A CN2007800087713 A CN 2007800087713A CN 200780008771 A CN200780008771 A CN 200780008771A CN 101400640 B CN101400640 B CN 101400640B
- Authority
- CN
- China
- Prior art keywords
- group
- methyl
- formula
- ethanoyl
- benzoyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
Disclosed is a method for producing a 1, 2-phenylethane compound with an extremely high yield through a short-time reaction. Specifically disclosed is a method for producing a 1, 2-phenylethane compound, wherein a compound represented by the formula (II) below is produced by subjecting a compound represented by the formula (I) below to a coupling reaction in the presence of a transition metal complex. [Chemical formula 1] (I) (In the formula, Ra represents a hydrogen atom or a substituted or unsubstituted phenyl group; Rb represents a hydrogen atom or a substituent, n represents an integer of 1-5, and when n is not less than 2, Rb's may be the same as or different from each other and may combine together to form a ring; and X represents a halogen atom.) [Chemical formula 2] (II).
Description
Technical field
The Patent of the application based on application on March 17th, 2006 advocated right of priority No. 2006-074463, here cites its content.
The present invention relates to the manufacture method of 1,2-diphenylphosphino ethane based compound, more specifically relate to and use transistion metal compound as 1 of catalyzer, the manufacture method of 2-diphenylphosphino ethane based compound.
Background technology
Four (hydroxy phenyl) alkane can be the host compound in inclusion compound as polymolecular.For example, 1,1,2,2-tetra-(4-hydroxy phenyl) ethane and various organic guest compound optionally form inclusion compound (having the compound that guest molecule enters the structure in the cavity that host molecule forms), so the application waited in expectation in the technical field of selective separation, chemical stabilization, non-volatileization, powdered etc.
So far, as the method for manufacturing four (hydroxy phenyl) alkane, known for example in acetic acid, under sulfuric acid exists, make the method (for example,, with reference to non-patent literature 1) of phenol and oxalic dialdehyde condensation in the temperature range of 2～10 ℃.
In addition, also known under hydrochloric acid exists, make the method (for example, referring to Patent Document 1) of oxalic dialdehyde and the greatly excessive phenol condensation with respect to oxalic dialdehyde in the temperature range of 100～180 ℃; Take the manufacture method (for example, referring to Patent Document 2) that makes four (hydroxy phenyl) alkane that phenol and the condensation of dialdehyde or derivatives thereof are feature in the presence of sulfuric acid and phosphoric acid.
Yet method as described in Patent Document 1 is the reaction under the sulfuric acid catalyst Individual existence like that, exist easily to occur that side reaction and reaction are easily out of hand etc. controls difficult problem.In addition, although use reaction under the high temperature of excessive phenol greatly to have not need, reaction solvent, reaction times are short, characteristics cheaply, exist side reaction easily occurs, and can't obtain high yield, and by the product of side reaction gained, being had multiplely, it removes very difficult problem.
In addition, as the method described in patent documentation 2, carry out condensation under existing by the mixed-acid catalyst at sulfuric acid and phosphoric acid, side reaction is inhibited, can efficiency optionally generate well four (hydroxy phenyl) alkane, but its yield is 40～70% left and right, reaction also need a few hours～tens of hours so long-time.
In addition, as the method described in patent documentation 3, by take the linked reaction that zinc is catalyzer, can manufacture the compound with the tetraphenyl skeleton that is combined with ester group on phenyl, but the method also will be refluxed and react about 24 hours, long reaction time and reaction yield are also low.
Non-patent literature 1:Monatshefte fur ChemIe., 82,652 (1951)
Patent documentation 1: JP 57-65716 communique
Patent documentation 2: Unexamined Patent 7-076538 communique
Patent documentation 3:WO00/20372
Summary of the invention
Problem of the present invention be to provide can be by the short period of time reaction, manufacture the method for 1,2-diphenylphosphino ethane based compound with high yield.
The inventor etc. have carried out concentrated research in order to address the above problem, found that by with transition metal complex, as catalyzer, carrying out the atom transferred free radical linked reaction, with coupling method, other synthesis method in the past of using zinc, compare, can and manufacture with high yield 1 with the very short reaction times, 2-diphenylphosphino ethane based compound, thus the present invention completed.
That is, the present invention relates to:
The manufacture method of 1,2-diphenylphosphino ethane based compound, is characterized in that, under the existence of transition metal complex, makes the compound shown in formula (I)
(Ra means hydrogen atom or replacement or unsubstituted phenyl, Rb means hydrogen atom or substituting group, n means 1～5 integer, n is 2 when above, Rb can be the same or different, can interconnect and form ring, X means halogen atom) carry out linked reaction, the compound shown in manufacture formula (II).
Above-mentioned [1] is described 1, and the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, Ra is for replacing or unsubstituted phenyl.
Above-mentioned [1] or [2] are described 1, and the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, the substituting group of the phenyl shown in Ra or the substituting group shown in Rb are COOR
1, SO
2r
2, OR
3, SR
4or N (R
5) (R
6) (R
1～R
6mean hydrogen atom or organic group).
In addition, the invention still further relates to:
Any one is described 1 in above-mentioned [1]～[3], and the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, the compound shown in formula (I) is the compound shown in formula (I-1);
Compound shown in formula (II) is the compound shown in formula (II-1).
Above-mentioned [4] are described 1, and the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, the Rb in formula (I-1) and formula (II-1) is OR
3or COOR
1.
Any one is described 1 in above-mentioned [1]～[5], and the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, transition metal complex is copper complex or iron complex.
Manufacturing method according to the invention can be manufactured 1,2-diphenylphosphino ethane based compound with high yield within the extremely short time.
Embodiment
As of the present invention 1, the manufacture method of 2-diphenylphosphino ethane based compound, so long as following method just is not particularly limited, that is, under the existence of transition metal complex, make formula (I)
Shown compound carries out linked reaction, manufacture formula (II)
Shown compound.According to the present invention, can obtain well in extremely short time internal efficiency the compound shown in formula (II).Compound shown in formula (I) can be used one or more, and linked reaction of the present invention can be can be also cross-coupling (cross-coupling) from coupling (homocoupling).
In formula (I) and formula (II), Ra means hydrogen atom or replacement or unsubstituted phenyl, from reactive angle, is preferably and replaces or unsubstituted phenyl.The substituting group of phenyl is 2, and this substituting group can be the same or different when above, can interconnect, and forms saturated rings, aromatic nucleus, heterocycle.Rb means hydrogen atom or substituting group.N means 1～5 integer, and n is 2 when above, and Rb can be the same or different, and can interconnect, and forms saturated rings, aromatic nucleus, heterocycle.In addition, X means halogen atom, can enumerate for example chlorine atom, bromine atoms, iodine atom, from reactive angle, is preferably bromine atoms.
As the substituting group of the phenyl shown in Ra or the substituting group shown in Rb, can enumerate for example COOR
1, SO
2r
2, OR
3, SR
4or N (R
5) (R
6), preferred COOR
1.R
1～R
6mean hydrogen atom or organic group, as organic group, can enumerate such as alkyl, silyl, acyl group, aryl, phosphoryl, alkylsulfonyl, alkyl phosphoryl, alkyl sulphonyl etc.Particularly, as substituting group, can enumerate the alkoxyl groups such as methoxyl group, oxyethyl group; The siloxyies such as trimethylsiloxy, t-butyldimethylsilyloxy base, 3,5-dimethylphenyl siloxy-; The acyl group such as ethanoyl, benzoyl; The aryloxy such as phenoxy group, naphthyloxy etc.
Especially can enumerate for example methyl, methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl (phenacyl), the cyclopropyl methyl, allyl group (allyl), sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl (anthrylmethyl), 4-picolyl (picolyl), trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl (valeryl), 2, 2, 2-tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, aryl-amino-carbonyl (aryl carbamoyl), methylsulfonyl, tosyl group etc.
As the compound shown in preferred formula (I), particularly, can enumerative (I-1)
Shown compound.
By carrying out the coupling of compound shown in this formula (I-1), can access formula (II-1)
Shown compound.
As the transition metal complex in the present invention, can enumerate the catalyzer that can use in living radical polymerization.In manufacture method of the present invention, can be to adding transition metal complex itself in system, also can form transition metal complex in system to interpolation metallic compound in system with as the compound of its ligand.
As the central metal that forms transition metal complex, can enumerate the periodic table of elements 7th～11 family's elements such as manganese, rhenium, iron, ruthenium, rhodium, nickel, copper (compiling the periodic table of elements of " I revision the 4th edition is compiled on chemical brief guide basis " (1993) record according to Japanization association).In these metals, preferably copper, iron, particularly preferably copper.
Particularly, as copper complex, can enumerate with NH
3, NO, NO
2, NO
3, quadrol, diethylenetriamine, tributylamine, 1,3-di-isopropyl-4,5-methylimidazole-2-pitches base (ylidene), pyridine, phenanthrolene, two phenanthrolenes, replace phenanthrolene, 2,2 ': 6 ', 2 "-tetra-pyridines, pyridine imine, crosslinked aliphatie diamine, 4-4 '-bis-(5-nonyl)-2,2 '-dipyridyl, thiocyanate ion, O, S, Se, the dipyridyl of Te coordination, the imido grpup dipyridyl, alkyl imido grpup pyridine, alkyl bipyridyl amine, alkyl replaces three pyridines, two (alkylamino) alkyl pyridine, the quadrol dipyridyl, three (pyridylmethyl) amine, N, N, N ', N ', N "-copper complex that the nitrogenous compound such as five methyl diethylentriamine and/or halogen atom are ligand, particularly, can enumerate ethanoyl [4-4 '-bis-(5-nonyl)-2,2 '-dipyridyl] and close copper, hexafluoro phosphine-bis-[4-4 '-bis-(5-nonyl)-2,2 '-dipyridyl] close copper, thiocyanato copper, [N, N, N ', N ', N "-five methyl diethylentriamine] cupric bromide etc.
As iron complex, can enumerate two (triphenylphosphine) ferrous chloride, two (tributyl amino) ferrous chloride, the triphenylphosphine iron trichloride, (1-bromine) ethylbenzene-triethoxy phosphine-dibrominated iron, (1-bromine) ethylbenzene-triphenylphosphine-dibrominated iron, (1-bromine) ethylbenzene-[4-4 '-bis-(5-nonyl)-2,2 '-dipyridyl] dibrominated iron, (1-bromine) ethylbenzene-tri--normal-butyl amino-dibrominated iron, (1-bromine) ethylbenzene-tri--normal-butyl phosphine-dibrominated iron, three-normal-butyl phosphine-dibrominated iron, [4-4 '-bis-(5-nonyl)-2,2 '-dipyridyl] dibrominated iron, tetra-allkylammonium three iron halide (II), dicarbapentaborane cyclopentadienyl ferric iodide (II), dicarbapentaborane cyclopentadienyl iron bromide (II), dicarbapentaborane cyclopentadienyl iron(ic) chloride (II), dicarbapentaborane indenyl ferric iodide (II), dicarbapentaborane indenyl iron bromide (II), dicarbapentaborane indenyl iron(ic) chloride (II), dicarbapentaborane fluorenyl ferric iodide (II), dicarbapentaborane fluorenyl iron bromide (II), dicarbapentaborane fluorenyl iron(ic) chloride (II), 1,3-di-isopropyl-4,5-methylimidazole-2-fork base iron(ic) chloride, 1,3-di-isopropyl-4,5-methylimidazole-2-fork base iron bromide etc.
And then, as other transition metal complex, can enumerate dichloro three (triphenylphosphine) and close ruthenium, dichloro three (tributylphosphine) closes ruthenium, dichloro (trialkyl phosphine) p-Methylisopropylbenzene closes ruthenium, two chloro-two (three (cymene) phosphine) styryl closes ruthenium, dichloro (cyclooctadiene) closes ruthenium, dichlorobenzene closes ruthenium, the dichloro p-Methylisopropylbenzene closes ruthenium, dichloro (norbornadiene) closes ruthenium, cis-dichloro two (2,2 '-dipyridyl) closes ruthenium, dichloro three (1,10-phenanthrolene) closes ruthenium, ruthenium is closed in carbonyl chlorine hydrogenation three (triphenylphosphine), chlorine cyclopentadienyl two (triphenylphosphine) closes ruthenium, chlorine indenyl two (triphenylphosphine) closes ruthenium, dihydro four (triphenylphosphine) closes ruthenium, dicarbapentaborane cyclopentadienyl iodate ruthenium (II), dicarbapentaborane cyclopentadienyl ruthenium bromide (II), dicarbapentaborane cyclopentadienyl ruthenium chloride (II), dicarbapentaborane indenyl iodate ruthenium (II), dicarbapentaborane indenyl ruthenium bromide (II), dicarbapentaborane indenyl ruthenium chloride (II), dicarbapentaborane fluorenyl iodate ruthenium (II), dicarbapentaborane fluorenyl ruthenium bromide (II), dicarbapentaborane fluorenyl ruthenium chloride (II), two is chloro-two-2, two [(the dimethylamino)-methyl] (μ-N of 6-
2) pyridine closes the ruthenium complexees such as ruthenium (II),
Carbonyl cyclopentadienyl nickelous iodide (II), carbonyl cyclopentadienyl nickelous bromide (II), carbonyl cyclopentadienyl nickelous chloride (II), carbonyl indenyl nickelous iodide (II), carbonyl indenyl nickelous bromide (II), carbonyl indenyl nickelous chloride (II), carbonyl fluorenyl nickelous iodide (II), carbonyl fluorenyl nickelous iodide (II), carbonyl fluorenyl nickelous bromide (II), carbonyl fluorenyl nickelous chloride (II), o, o '-bis-(dimethylamino methyl) phenyl nickel halogenide, two-triphenylphosphine Nickel Bromide, two (three normal-butyl amino) Nickel Bromide, 1, 3-diamino-phenyl nickelous bromide, two (tri-n-butyl phosphine) Nickel Bromide, four (triphenylphosphines) close the nickel complexes such as nickel,
Three carbonyl cyclopentadienyl molybdenum iodides (II), three carbonyl cyclopentadienyl molybdenum bromides (II), three carbonyl cyclopentadienyl molybdenum chlorides (II), two (N-aryl)-bis-(2-dimethylamino methyl phenyl) lithium molybdenums, two (N-aryl)-(2-dimethylamino methyl phenyl)-methyl-lithium molybdenum, two (N-aryl)-(2-dimethylamino methyl phenyl)-trimethyl silyl methyl-lithium molybdenum, two (N-aryl)-(2-dimethylamino methyl phenyl)-p-methylphenyl-molybdenum matchs such as lithium molybdenum; The tungsten complexes such as three carbonyl cyclopentadienyl tungsten iodides (II), three carbonyl cyclopentadienyl tungsten bromides (II), three carbonyl cyclopentadienyl tungsten chlorides (II); The dicarbapentaborane cyclopentadienyl closes the cobalt complexes such as cobalt (I); Three carbonyl cyclopentadienyls close manganese (I), three carbonyls (methyl cyclopentadienyl) close the manganese complexes such as manganese (I); Three carbonyl cyclopentadienyls close the rhenium compounds such as rhenium (I), two (triphenylphosphine) iodate rheniums of dioxo; The rhodium complexs such as three (triphenylphosphine) rhodium chloride; The triphenylphosphine diacetyl closes palladium complexes such as palladium etc.These transition metal complexes can be used one or more to be used in combination.
As the addition of transistion metal compound, by its kind, determined, general with respect to the compound shown in the formula as raw material (I), be preferably 0.1～5 equivalent, more preferably 0.3～1 equivalent.
In addition, in manufacture method of the present invention, from the viewpoint of the activity that can realize improving catalyzer, preferably under the existence of alkali, carry out linked reaction.As alkali, can be that organic bases can be also mineral alkali, as organic bases, can enumerate amines such as fatty amine, aromatic amine, as mineral alkali, can enumerate such as the oxide compound of alkali metal hydroxide or carbonate, alkaline-earth metal or carbonate etc.
Be not particularly limited as the organic solvent used in reaction, can enumerate such as benzene,toluene,xylene etc. aromatic hydrocarbon based; The aliphatic hydrocarbons such as hexane, heptane, octane; The alicyclic hydro carbons such as pentamethylene, hexanaphthene, cyclooctane; The ketones such as acetone, methyl ethyl ketone, pimelinketone; The ethers such as tetrahydrofuran (THF), dioxane; The ester such as ethyl acetate, butylacetate class; The amides such as DMF, N,N-dimethylacetamide; The sulfoxide types such as dimethyl sulfoxide (DMSO); The alcohols such as methyl alcohol, ethanol; The polyol derivative such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate class etc.These solvents can be used separately a kind of, or can be used in combination of two or more.
Temperature of reaction is generally room temperature～150 ℃, is preferably 60～120 ℃.Reaction is usually at normal pressure or add to depress and carry out.In addition, reaction was carried out with the extremely short time, 3～90 minutes, preferably about 5～30 minutes, complete.Like this, manufacturing method according to the invention, can the utmost point manufacturing objective compound efficiently.The termination of reaction can descend by the temperature that makes reaction system to carry out.Reaction can carry out the separate targets compound by general separation purification method such as recrystallization, column purification, decompression purifying, filtrations after finishing.
In addition, in manufacture method of the present invention, the compound shown in the formula of manufacturing (II) has COOR as above on phenyl ring
1, SO
2r
2, OR
3, SR
4or N (R
5) (R
6) and so on substituting group the time, can implement acid treatment and become reactive hydrogen next life, substituting group is separately converted to COOH, SO
2h, OH, SH or NH
2.In addition, be converted into OH, SH base after can being hydrolyzed under alkali exists.As the acid of using in acid treatment, can enumerate the mineral acids such as hydrochloric acid, bromic acid, sulfuric acid, nitric acid, boric acid, methylsulfonic acid; The organic acids such as acetic acid.Acid-treated treatment temp is not particularly limited, and can carry out the scope of for example-10 ℃～150 ℃.As alkali, can be that organic bases can be also mineral alkali, as organic bases, can enumerate amines such as fatty amine, aromatic amine, as mineral alkali, can enumerate such as the oxide compound of alkali metal hydroxide or carbonate, alkaline-earth metal or carbonate etc.
Below, be described more specifically the present invention by embodiment, but technical scope of the present invention is not limited to these examples.
Embodiment 1
Add PhCOOEt in the 50ml flask
2-Br 0.39g (1mmol), CuBr 0.14g (1mmol), Cu (0) 0.25g (4mmol), toluene 20ml, degassed.Add again N, N, N ', N ', N "-five methyl diethylentriamine 0.35g (2mmol), at 80 ℃, stir 30 minutes.After reaction solution is cooling, filter insolubles.Washing filtrate in water layer decoloration, use MgSO
4carry out drying.Distillation, except after desolventizing, is under reduced pressure carried out drying, obtains white crystals 0.30g (separation yield 97%).
Embodiment 2
In the 30ml flask, add 4-(brooethyl) methyl benzoate 1.15g (5mmol), CuBr0.72g (5mmol), Cu (0) 1.27g (20mmol), dipyridyl 1.56g (10mmol), toluene 20ml and degassed after, at 100 ℃, stir 1 hour.After reaction solution is cooling, add chloroform 10ml, filter insolubles.After washing filtrate, use MgSO
4carry out drying.Distillation, except after desolventizing, is carried out recrystallization by ethyl acetate/hexane.Drying is under reduced pressure carried out in the gained crystallization, obtains faint yellow crystallization 0.32g (separation yield 43%).
Embodiment 3
In the 200ml flask, pack into two (4-hydroxy phenyl) methane 9.6g (48mmol), triethylamine 11.8g (117mmol), tetrahydrofuran (THF) 200ml, be cooled to 0 ℃.Add wherein Benzoyl chloride 14.9g (106mmol), at room temperature stir 1 hour.After removing by filter the triethylamine hydrochloride, that filtrate is concentrated.After dissolving with methylene dichloride, wash three times, with sal epsom, carry out drying.After reaction solution is concentrated, carry out recrystallization by hexane/ethyl acetate, thereby obtain faint yellow needle crystal A 16.8g (separation yield 86%).
In the 200ml flask, pack into just now synthetic A 14.4g (35mmol), N-bromosuccinimide 6.5g (37mmol), benzene 70ml, reflux 1 hour.After cooling, that reaction solution is concentrated.After dissolving with methylene dichloride, wash three times, with sal epsom, carry out drying.After reaction solution is concentrated, carry out recrystallization by ethyl acetate, thereby obtain white cotton-shaped crystallization B 11.7g (separation yield 68%).
In the 100ml flask, pack into just now synthetic B 4.9g (10mmol), CuBr 0.7g (5mmol), Cu 1.3g (20mmol), toluene 50ml, degassed.After being heated to 80 ℃, add N, N, N ', N ', N "-five methyl diethylentriamine 1.8g (10mmol), at 80 ℃, stir 30 minutes.By the reaction solution cooled and filtered, by insolubles washing three times.Add chloroform 100ml in insolubles, after refluxing 10 minutes, filtered while hot.After filtrate is concentrated, with the ethyl acetate washing, thereby obtain white cotton-shaped crystallization C 3.1g (separation yield 76%).
Then, just now synthetic C 2.6g (3.2mmol), toluene 50ml pack in the 100ml flask, the hydrolysate that will under the existence of potassium hydroxide, water, carry out saponification and obtain carries out purifying, obtain 1,1, the white powder 1.1g (2.8mmol) of 2,2-tetra-(4-hydroxy phenyl) ethane D.
Claims (3)
1. the manufacture method of a 2-diphenylphosphino ethane based compound, is characterized in that, under the existence of copper complex, makes the compound shown in formula (I)
Carry out linked reaction, the compound shown in manufacture formula (II),
In formula, Ra is illustrated in contraposition by being selected from COOH, SO
2h, OR
3, SH, NH
2, the substituting group in COOEt, methoxyl group, oxyethyl group, trimethylsiloxy, t-butyldimethylsilyloxy base, 3,5-dimethylphenyl siloxy-, ethanoyl, benzoyl, phenoxy group or the naphthyloxy phenyl or the unsubstituted phenyl that replace, R
3mean hydrogen atom or be selected from methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl, cyclopropyl methyl, allyl group, sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl, 4-picolyl, trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl, 2, organic group in 2,2-, tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, methylsulfonyl, tosyl group; Rb means hydrogen atom or is selected from COOH, SO
2h, OR
3, SH, NH
2, the contraposition in COOEt, methoxyl group, oxyethyl group, trimethylsiloxy, t-butyldimethylsilyloxy base, 3,5-dimethylphenyl siloxy-, ethanoyl, benzoyl, phenoxy group or naphthyloxy substituting group, R
3mean hydrogen atom or be selected from methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl, cyclopropyl methyl, allyl group, sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl, 4-picolyl, trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl, 2, organic group in 2,2-, tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, methylsulfonyl, tosyl group; N means 1 integer, and X means halogen atom.
2. according to claim 11, the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that,
Compound shown in formula (I) is the compound shown in formula (I-1);
Rb means hydrogen atom or is selected from COOH, SO
2h, OR
3, SH, NH
2, the substituting group in COOEt, methoxyl group, oxyethyl group, trimethylsiloxy, t-butyldimethylsilyloxy base, 3,5-dimethylphenyl siloxy-, ethanoyl, benzoyl, phenoxy group or naphthyloxy, R
3mean hydrogen atom or be selected from methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl, cyclopropyl methyl, allyl group, sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl, 4-picolyl, trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl, 2; 2; organic group in 2-tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, methylsulfonyl, tosyl group; X means halogen atom
Compound shown in formula (II) is the compound shown in formula (II-1),
Rb means hydrogen atom or is selected from COOH, SO
2h, OR
3, SH, NH
2, the substituting group in COOEt, methoxyl group, oxyethyl group, trimethylsiloxy, t-butyldimethylsilyloxy base, 3,5-dimethylphenyl siloxy-, ethanoyl, benzoyl, phenoxy group or naphthyloxy, R
3mean hydrogen atom or be selected from methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl, cyclopropyl methyl, allyl group, sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl, 4-picolyl, trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl, 2; organic group in 2,2-, tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, methylsulfonyl, tosyl group.
3. according to claim 21, the manufacture method of 2-diphenylphosphino ethane based compound, is characterized in that, the Rb in formula (I-1) and formula (II-1) is OR
3, COOH or COOEt, R
3mean hydrogen atom or be selected from methyl, methoxymethyl, 2-methoxy ethoxy methyl, methylthiomethyl, THP trtrahydropyranyl, phenacyl, cyclopropyl methyl, allyl group, sec.-propyl, cyclohexyl, the tertiary butyl, benzyl, adjacent nitrobenzyl, 9-anthryl methyl, 4-picolyl, trimethyl silyl, t-butyldimethylsilyl, ethanoyl, benzoyl, pentanoyl, 2; organic group in 2,2-, tri-chloroethyl carbonyls, vinyl carbonyl, benzyloxycarbonyl group, methylsulfonyl, tosyl group.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP074463/2006 | 2006-03-17 | ||
| JP2006074463 | 2006-03-17 | ||
| PCT/JP2007/055393 WO2007119402A1 (en) | 2006-03-17 | 2007-03-16 | Method for producing 1,2-phenylethane compound using atom transfer radical coupling reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101400640A CN101400640A (en) | 2009-04-01 |
| CN101400640B true CN101400640B (en) | 2013-05-08 |
Family
ID=38609193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800087713A Expired - Fee Related CN101400640B (en) | 2006-03-17 | 2007-03-16 | Method for producing 1,2-phenylethane compound using atom transfer radical coupling reaction |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8034971B2 (en) |
| EP (1) | EP1997798A4 (en) |
| JP (1) | JP5081146B2 (en) |
| CN (1) | CN101400640B (en) |
| WO (1) | WO2007119402A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110015960A (en) * | 2019-05-08 | 2019-07-16 | 大连大学 | The preparation method and application of 1,3- bis- (4,4- methyl formate phenyl) acetone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1120391B1 (en) * | 1998-10-08 | 2008-08-06 | Nippon Soda Co., Ltd. | Molecular compounds containing novel carboxylic acid derivatives as the constituent compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5765716A (en) | 1980-10-08 | 1982-04-21 | Mitsubishi Petrochem Co Ltd | Curing of thermosetting resin composition |
| JP3461014B2 (en) | 1993-09-07 | 2003-10-27 | 日本曹達株式会社 | Method for producing tetrakis (hydroxyphenyl) alkane |
| AU1127700A (en) * | 1998-10-20 | 2000-05-08 | Omeros Medical Systems, Inc. | Irrigation solution containing mapk inhibitors and their use for treating pain and inflammation |
| JP4110478B2 (en) | 2004-09-02 | 2008-07-02 | ソニー株式会社 | Image processing apparatus and method, photographing apparatus, and program |
-
2007
- 2007-03-16 WO PCT/JP2007/055393 patent/WO2007119402A1/en active Application Filing
- 2007-03-16 JP JP2008510801A patent/JP5081146B2/en not_active Expired - Fee Related
- 2007-03-16 EP EP07738838A patent/EP1997798A4/en not_active Withdrawn
- 2007-03-16 CN CN2007800087713A patent/CN101400640B/en not_active Expired - Fee Related
- 2007-03-16 US US12/225,217 patent/US8034971B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1120391B1 (en) * | 1998-10-08 | 2008-08-06 | Nippon Soda Co., Ltd. | Molecular compounds containing novel carboxylic acid derivatives as the constituent compound |
Non-Patent Citations (4)
| Title |
|---|
| KernJ-M et al.Photoassisted C-C coupling via electron transfer to Benzylic Halides by a Bis(di-imine) Copper(I) complex.《Journal of the chemical society, chemical communications》.1987,第8卷(第1期),546-548. * |
| Khurana, Chauhan, Maikap.Facile reductive coupling of benzylic halides with ferrous oxalate dehydrate.《Organic and biomolecular chemistry》.2003,第1卷1737-1740. * |
| Li，Kijima，Izumi.Ruthenium-catalyzed carbon-carbon formation to synthesize tetraarylethanes and tetraarylxylylene through dechlorinative dimeric reaction.《Journal of organometallic chemistry》.2003,第687卷12-15. * |
| Osako et al.Carbon-Halogen bond activation mechanism by Copper(II) complexes of (2-Pyridyl)-alkylamine ligands.《Chemistry Communications》.2005,第44卷(第2期),410-415. * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1997798A1 (en) | 2008-12-03 |
| JPWO2007119402A1 (en) | 2009-08-27 |
| EP1997798A4 (en) | 2010-09-29 |
| WO2007119402A1 (en) | 2007-10-25 |
| JP5081146B2 (en) | 2012-11-21 |
| CN101400640A (en) | 2009-04-01 |
| US20090275772A1 (en) | 2009-11-05 |
| US8034971B2 (en) | 2011-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047198B (en) | Method for preparing polyaryl substituted naphthalene derivative by reaction of aryl ketone and tolane under catalysis of ruthenium | |
| US11530230B2 (en) | Compound of 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphine ligand, and preparation method thereof | |
| JPH10502387A (en) | Heteroaromatic diphosphines as chiral ligands | |
| JP4636889B2 (en) | FULLERENE DERIVATIVE, FULLERENE METAL COMPLEX, AND METHOD FOR PRODUCING THEM | |
| KR101787211B1 (en) | a new palladium catalyst, method for its preparation and its use | |
| CN101400640B (en) | Method for producing 1,2-phenylethane compound using atom transfer radical coupling reaction | |
| US8198471B2 (en) | 2, 2′-bis (dialkylphosphino) biphenyl compound, production method thereof, and metal complex comprising the compound as ligand | |
| Yang et al. | Enantioselective addition of phenylacetylene to aldehydes catalyzed by 1, 3-aminophenol ligand | |
| JP5208939B2 (en) | 2,2 ', 6,6'-tetrasubstituted aminophosphine ligand and method for synthesis thereof | |
| Drabina et al. | Synthesis, copper (II) complexes and catalytic activity of substituted 6-(1, 3-oxazolin-2-yl) pyridine-2-carboxylates | |
| Jiao et al. | A series of acac-ruthenium complexes with chiral Schiff base ligands: Synthesis, characterization and catalytic property | |
| KR100838122B1 (en) | Palladium Pincer Complexes and a Manufacturing method thereof | |
| JP2008069104A (en) | Helicene derivative, triyne derivative and method for producing the helicene derivative | |
| Aroz et al. | One-pot self-assembly of trinuclear silver (I) clusters containing propargyl alcohols and bis (diphenylphosphino) methane (dppm) ligands | |
| JP5265640B2 (en) | FULLERENE DERIVATIVE, FULLERENE METAL COMPLEX, AND METHOD FOR PRODUCING THEM | |
| JP2019104716A (en) | Organic metal iridium complex, synthetic method thereof, and organic light-emitting element using the same | |
| JP2004196710A (en) | Ligand and asymmetric catalyst | |
| JP4982732B2 (en) | Binaphthyl derivative and method for producing the same | |
| JP2018135292A (en) | Method for producing optically active alcohol and asymmetric catalyst | |
| JP6625013B2 (en) | Bisphosphimino ligand having a binaphthol skeleton and catalyst using the same | |
| JPWO2008059960A1 (en) | Method for producing quarterpyridine derivative and its intermediate | |
| JP4902952B2 (en) | Chiral phosphane for use in asymmetric synthesis | |
| JP6263815B2 (en) | Cell death inhibitor and method for producing the same | |
| JP4182242B2 (en) | Optically active azetidine methanol phosphine coordination transition metal complexes, intermediates, processes and applications | |
| JP2012031119A (en) | Axially chiral isoquinoline derivative, its production method, and asymmetric synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130508 Termination date: 20180316 |